Process for preparing epoxide compounds

ABSTRACT

A COMPOUND REPRESENTED BY THE FORMULA:   O&lt;(-CH(-CO-CH3)-C(-CH3)2-)   IS PREPARED BY REACTING ACETONE IN THE PRESENCE OF (CUOCH3)CL-PYRIDINE.

compound represented by the formula:

unimd S ates Patent 2 Claims ABSTRACT OF THE DISCLOSURE C\-CHCOCH| C 0is prepared by reacting acetone in the presence of (CuOCH )Cl-pyridine.

The present invention refers to a process for preparing epoxidecompounds and to the products obtained thereby.

It is known that divalent copper compounds are reduced to monovalentcopper compounds by means of carbonyl compounds. This reaction isgenerally carried out on the copper halides, whereas the carbonylcompounds are the organic compounds containing the CO group as aldehydesand ketones. When a compound as aforesaid, selected from the class ofthe ketones, is reacted with a divalent copper compound, preferably ahalide compound, this latter is reduced to monovalent copper compoundand the ketone compound is converted into an alpha-halogenketone.

We have now surprisingly found that epoxide compounds may be obtainedstarting from at least a carbonyl compound having the formula:

compounds (b) containing halogen atoms which are reduced to monovalentcopper compounds and corersponding to the formula:

Cu(OR)X-L wherein R is a hydrocarbon radical having up to 20 carbonatoms; X is a halogen as chlorine, bromine, iodine and fluorine, and ananion as ON, -OCOCH enolate, nitrate and the like; L is a substituted orunsubstituted coordinating base selected among phenantroline, dipyridyl,pyridine, dimethylsulphoxide (DMSO), dimethylformamide (DMF),phosphines, arsines, stibines and imidazole; n is a number rangingbetween 0 and 4. The same behaviour is shown by the analogous compoundsof Hg, Al, Co and T1.

3,773,798 I Patented Nov. 20, 1973 "ice wherein the symbols have theaforesaid meanings. Particularly it is to be noted that the above schemeshows a reaction between two moles of the same carbonyl compound, but itis clear that the reaction may be carried out also between two dilferentcarbonyl compounds.

The inventive process is simply carried out; it proceeds with goodyields and may be carried out in a large range of pressures andtemperatures. The reaction maybe realized either with solvents orwithout any solvent and diluent. According to the latter one the samecarbonyl compound is acting as reaction medium. When employing a solventit may be selected from alcohols, glycols, hydrocarbons, halogenatedsolvents as carbon tetrachloride, benzene monochloride or dichloride,ethers as dioxane, tetrahydrofurane, glycols ethers, pyridine,picolines, quinolines, dimethylsulphoxide, dimethylformamide, etc.

As to the reaction temperatures, they do not influence the reactioncourse provided that the liquid phase is maintained as such; thepressure too may be selected in a wide range provided that the liquidphase is always such. Illustrative values of temperatures and pressurepreferably selected according to the invention are the ones selectedfrom the range comprised between the room temperature and C. as to thetemperatures, and comprised between 1 and 20 atmospheres as to thepressures.

The copper compounds are obtained according to well known methods. Forexample, the compound Cu(OCH Cl-Py (Py=pyridine) may be obtained byoxidizing CuCl in methyl alcohol containing the pyridine amountnecessary to the complex forming. On the contrary, it is possible toobtain the copper compound by means of a change reaction between CuCl-Py and methyl alcohol in presence of stoichiometric amounts of alkalinehydroxides as KOH, LiOH and the like.

The copper compound reacting with the carbonyl compound may be preformedand then fed to the reaction vessel, but it may be obtained also duringthe course of the reduction reaction. In the latter case the carbonylcompound is fed to the reaction vessel, wherein the divalent coppercompound is being formed, it being reduced while being formed. Aremarkable matter of the inventive process is given by the chance ofeasily obtaining the divalent copper compound from the reduced coppercompound.

As divalent compounds, use is made of the alkoxyhalide metal complexesselected among the alkoxy, arylalkoxy and phenoxy compounds;particularly it may be an unsaturated or substituted one too, obtainedfrom glycols or glycol ethers chloridines, cyano-alcohols, nitroalcohols and oxyesters.

As carbonyl compounds aldehydes, diketones and ketoaldehydes, although apreferable use is made of the ketones selected among the dialkylketones,the substituted or unsubstituted aryl-alkyl-ketones, the acyclic orcyclic ketones in which rings are formed by intramolecular reactions,and generally the compounds in which the two reacting groups belong tothe same molecule and may undergo intramolecular reactions bringing tocyclic epoxide compounds through forming new C-C bonds.

3 The following examples are reported in order to better illustrate theinvention without limiting it at all.

EXAMPLES Variousamounts of (CuOCH )Cl-Py-as a divalent copper compoundof a type useful according to the invention-were prepared by means ofboth the aforesaid methods. 2.5 g. of said compounds were suspended into15 cc. of the ketone and maintained at 60 C. under nitrogen, for a timevarying as regards to the ketone type (/2 hour for cyclopentanone and 7hours for acetone). The reaction end could be visually verified by theformation of a low-yellow precipitate or of a brown-yellow solution. Bycooling the highest amount of the complex was recovered as CuClPy. Theketone excess was removed under vacuum and the residue was subjectedeither to a fractional distillation under vacuum or to acrystallization. The reaction products obtained were:

o---cH-000H, C \O/ Uncoloured liquidT =5960 C. at 17 mm. Hg M.W=114 Ithad the same mass spectrum and same NMR of the pure product obtained bysynthesis. It was obtained with a yield of 70% with respect to copper.

, n 4 By working according to-"the same proce are, it was possible toobtainepoxide starting frorn acetophenone;

M.W.=238: A mixture of the cis and trans isomers, which were separatedas follows:

trans: M.P.=163164 C. It crystallized from acetone as the first one.

cis: M.P.=89-91 C. Itcrystallizedfrom ligroin as the first one.

The total yield of the two isomers is w th respect to copper. 7 1 Whatwe claim is: 1 1. A process for the formation of the compound:

/C\CHCOCH| CH3 0/ which comprises reacting acetone in the'ipresence of(CuOCHQCl-pyridine until said compound is formed, and thereafter,separating and recovering said compound. 2. A process as defined byclaim 1 which is carried out under nitrogen.

No references cited.

NORMA S. MILESTONE, Primary Examiner

